Friedel-crafts isobutylene polymerizations in chlorofluoroalkane solution



Patented July 7, 1953 7 P w -FRIEDEL-CRAFTS ISOBUTYLENE POLY- MERI ZATIONS IN GHLOROFLUORO- ALKANE SOLUTION John S. Saylor, JL, Sinking Spring, Pa., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application January 11, 1950,-

Serial No. 138,063

This invention relates to low temperature polymerization processes for olefinicmaterial, relates particularly to the low temperature polymerization of mixtures of olefins and mono-olefins, and relates especially to low temperature olefinic poly merization in the presence of chloro-fiuoro substituted alkanes which are non-solvents for and insoluble in the olefinic polymer, are solvents for, and mixable with, the olefinic monomers, are liquid at the polymerization temperature and by their presence modify the copclymerization ratio in such a Way as to increase the unsaturation cf the copolymer from a given polymerizate mixture,

and simultaneously prevent coalescence ofipartie cles of polymer into large masses. e v

This application is a continuation-in-part of my copending applications, Serial'No. 502,438, filed September 15,1943, now abandoned, and erial No. 556,658, filed September 30, 1944, which issued January 1'7, 1950 as U. S. 2,494,585.

It has been found possible to polymerize cle- 8 Claims. (Cl. 260-:85-3) fins such as isobutylene in admixture with a polyolefin such as butadiene or isoprene or the like at temperatures ranging from C. to 1'00 C., or even as low as -16? C. by the applica' tion thereto of a Friedel-Crafts catalyst, preferably in solution in a low-freezing, non-complexforming solvent to yield a highly valuable synthetic substitute for rubber, However, the re: action is difiicult to control and difiicult to conduct because of the thick, heavy, gummy character of the polymer both at the low temperature of polymerization and at room temperature; and

the chloro-flucro -substituted alkane compound be present as a fugitive solid, but that if it is present as a liquid, in the substantial absence of other inert diluents (except for small amounts of catalyst solvent), the polymer remains dispersed in the reactor liquid in satisfactorily small particles, and the resulting polymer has properties which are still better than those produced by my previously disclosed processes. The best results are obtained from a material in which thereis present only the unsaturates, the catalyst (preferably in solution), and the chlorofluoro-substituted compounds, but practically as good results are obtained when the catalyst is added in solution in comparatively small amounts of a'chloro alkane such as methyl or ethyl chloride, but still better results are obtained if the catalyst also is dissolved in a fluoro-substituted alkane as shown in the copendingapplication of Welch and Wilson, Serial No. 64,236, filed December 8, 1948. v

The copclymer of isobutylene'with a multiclefin such as isoprene or butadieneor the like has been produced from several different types of mixtures. isobutylene and diolefin can be polymerized as such, by the addition of liquid catalyst to the coldmixed unsaturates in the absence of significant amounts of diluent. When the reaction is conducted underthese conditions, the polymerization ratio between the isobutylene and diole- 'fin tends to be relatively high, the molecular weight tends to be somewhat low, and the iodine great difficulty has been encountered in develOping a process which was both simple to operate and at the same time yielded a high grade polymer.

My previous application for patent, Serial No. 556,658, new Patent No. 2394,5255 showed that if the polymerization was conducted in the presence of a fugitive solid, in a kneader, the solid, under the influence of the kneader plates ex: erted a grinding action upon the polymer, whereby the polymer was broken up .into small'fr agments, especially in the presence of a diluent such as methyl chloride or the like] The combination of results were obtained that the formation of large chunks of polymer was avoided, and the resulting polymer showed much superior ten.- sile strength and other improved properties.

It is now found, according to the presentinvention, that substantially better'results are obtainable by the use of the chloro fiuoro-com pound in liquid form. According to thefpresent invention it is found that it is not necessary that number tends to be relatively high, but not as high as the proportion of copolymerized diolefin would indicate. Also, considerable amounts of polymer are producedwhich are foundtube insoluble in solvents, these two phenomena together indicating the presence-of an excessive amountof' cross-linkage in the polymer. The relatively low molecular weight, the presence of insoluble material and the generally poor character of non-diluent polymer has caused this process to be regarded as unsatisfactory. The

presence of a diluent such as the light naphthas modify the copolymerization ratio to reduce sharply the proportion of diolefin to isobutylene, and to remove substantially completely all tendency towards cross-linkage, but the process is exceedingly difiicult to operate because of the inordinately high viscosity of polymer solutions in hydrocarbons, especially at the polymerization temperature. The use of a diluent for the polymerization which is a non-solvent for the completed polymeryields a commercial process For instance, the cold mixture of in which the polymer is produced as a slurry of relatively low viscosity, and substantially no cross-linked polymer is produced, but the ratio of diolefin to isobutylene is undesirably low, and the iodine number also is undesirably low. Polymerization in the presence of a fluoro alkane in which both the olefinic monomers and thepolymer are insoluble yields a slurry of polymer which can be handled, but the characteristics of the polymer are undesirably close to those obtained from the simple mixed monomers in the absence of diluent.

According to the present invention, it is now found that if a chloro-fluoro alkane compound, in which the monomers are soluble and the polymer insoluble, is used, the unexpected and valuable efiect is obtained that the copolymerization ratio of diolefin to isobutylene is relatively high, substantially no cross-linkage occurs and the iodine number obtainable from a given proportion of diolefin to isobutylene is also desirably high. The resulting copolymer shows the interesting and valuable property of significantly and substantially higher cure rate than is obtainable by any other procedure.

Thus the invention provides a new and useful combination of elements, utilizing as the copolymerizate material, a mixture of a major proportion of isobutylene with a minor proportion of a multi-olefin in the presence of a chlorofiuoro-substituted alkane polymerized at temperatures within the range between about 20 C. and l64 C. 1

Other objects and details of the invention will be apparent from the following description.

In practicing the invention, any convenient type of reactor may be used, such as a kneader of the general character of the so-called Werner- Phleiderer type, or the commercially standard refrigerant jacketed cylinder for continuous operation. In the kneader, the kneader blades provide an excellent agitation of the polymerizate mixture, especially when operated at relatively high rotational speeds; in the cylindrical type of commercial reactor a large propeller-type stirrer likewise provides ample agitation and circulation of the material. The reactor may then be charged with the desired isobutylene-multi olefin mixture together with a suitable chlorofiuoro-substituted alkane, the mixture being then treated with a Friedel-Crafts catalyst at a temperature within the range between 20 C. and -16-i C., preferably within the range between about 70 C. and 103 C. It is of the essence of the present invention that the chloro-fluoro alkane shall be liquid at the polymerization temperature and it. is preferable that it shall be volatile at a temperature below the boiling point of water, or preferably that it shall be volatile at a temperature below room temperature.

The preferred. substance is the dichlorodifiuoromethane. Other suitable substances are shown in the following table:

These substances are the preferred ones of a considerable .number of fluoro-substituted aldegree of insolubility for the copolymer.

kanes which are satisfactory for the purposes of the present invention.

It may be noted that all of these substances are non-reactive in the polymerization reaction, all show a very low solubility for and solubility in the polymer, and all are solvents for, and readily mixable with isobutylene and the multi-olefins in the olefinic mixture.

By this combination of components with the stated characteristics, the unexpected and very valuable result then appears-that the solid polymer is produced in very small particles which show very little tendency to coalesce into lumps or adhere to the walls of the reactor, thereby maintaining an excellent slurry of small solid polymer particles in the fluoroalkane through the entire polymerization reaction, and through the Warming up stage as well as in a water slurry; at the same time the properties of polymer when cured are markedly improved especially in curing speed because of the very unusual and unexpected phenomenon that a higher amount of unsaturation is obtainable in the finished polymer from a given mixture of isobutylene and multiolefin than is obtainable by any other procedure; this increase in unsaturatio-n varying from an increase of 10% to an increase of nearly this improvement being particularly well shown in the continuous reactor where a portion only of the unsaturates are copolymerized. Also, a very sharply reduced amount of polymer adheres to the inner walls of the reactor, especially in the cylindrical continuous reactor. These advantages appear to be due in part to the high insolubility of the polymer in the chloro-fluorosubstituted alkanes, and the very low solubility of the alkanes in the polymer.

It may be noted'particularly that the chlorofluoro compounds show an excellent solubility for and mixable with the olefinic monomers, when used as reactant dilucnts, and show a very high This combination of properties thus makes possible the preparation of a conveniently concentrated solution of monomers in diluent, which, after polymerization yields an excellent slurry of polymer in the chloro-fluoro alkane.

The fact that many of the chloro--fluorinc containing alkyl compounds have boiling points above room temperature, and an extremely low solvent power for and solubility in the polymer permits of a ready separation of the solid polymer from the slurry or emulsion in the alkyl chloro-fiuoro compound, at room temperature by a relative simple filtration procedure. In bringing the temperature from polymerization temperature to room temperature, practically all of the olefinic polymerization mixture substances present volatilize away from the polymer substantially completely, leaving behind enough liquid alkyl chlorofluoride to maintain the suspension, from which the polymer is easily recovered by a filtration procedure followed by washing with water, for milling atan elevated temperature, to remove the last of the liquid material.

For the polymerization procedure, the reactor is cooled to a polymerization temperature ranging from -20 C. down to 164 C. depending upon the refrigerant used. To the cold reactor there is then added the desired polymerizable olefinic material.

This material preferably consists of isobutylene but in some instancesmay consist of a higher isoolefln such as Z-methyl, butene-l or Z-methyl,

.pentene-l or Z-methyl, hexene-l, iso-octene or the like; in admixture with a polyolefln such as butadiene or isoprene or piperylene or dimethallyl (also known as diisobutyenyl) or myrcene or the like. These are the preferred polyolefins but substantially any of the polyolefins having from 4 to 14 carbon atoms per molecule are useful. The isoolefin is preferably present in major proportion and the polyolefin in minor proportion; the best proportions lying within the range from 70 parts to 99.5 parts of the isoolefin with 30 parts to0.5 part of the polyolefin. Alternatively, however, especially when butadiene is used, the butadiene may be present in the copolymerizate mixture in an amount from one equal to theamount of isobutylene present, to eight or nine times as much, as shown in the copending application of Nelson and Welch, Serial No. '788,640, filed November 28, 1947.

The polymerization is conducted by applying to the olefinic material in the reactor a Friedel- Crafts catalyst, preferably in solution in a low freezing non-complex forming solvent. The preferred-catalyst material is aluminum chloride in solution in ethyl or methyl chloride or carbon di-' sulfide. However, substantially any of the Friedel-Crafts catalysts disclosed by N. O. .Calloway in his article on The Friedel-Crafts synthesis, printed in the issue of Chemical Review, published for the American Chemical Society at Baltimore in, 1935, in volume XVII, No. 3, the article beginning on page 327, the list being particularly well shown on page 375, may be used. All of the-other catalysts may be dissolved inthe solvent if desired. For the solvent substantially any of the mono or poly alkyl halides which have freezing points below 0 C., thereby having low freezing with respect to water, may be used. Alternatively, carbon disulfide may be used, all or these solvents being characterized by their freedom from any tendency toform a complex with the Friedel-Crafts halide, as shown bythe fact that the solvent can be volatilized away from the solute substantially completely without any sig 95% or even 100% polymerization of the -isoolefin and polyolefin, the material is removed from the reactor and brought up to room temperature; preferably by discharging the reactor contents into warm water or warm alkali solutainable iodine number from the same proportion of diolefin to isobutylene when polymerized according to the process of the prior art.

The material may then be compounded with' 1 such substances as sulfur, zinc oxide, stearic acid, carbon black and the like, and cured at appropriate temperatures and times.

The resulting cured polymer shows an excellent. tensile strength ranging from 1800 pounds to 4500 pounds per square inch; an elongation at break of from'300% to 1200%; good processing characteristics for such operations as milling, calendering, extruding and the like; a very desirably low heat build-up under rapid flexure; a high abrasion and flexure resistance, and many other very valuable physical properties. In addition, the polymer shows a very valuable increase in speed of curing.

Example 1.

A series of polymerizati'ons were conducted using different amounts of diluent in the form of,

difiuorodichloromethane and different concentrations of catalyst, the amount of alkane chlorofiuoride varying between about one volume per volume of mixed olefins to about 10 volumes per volume of mixed olefins.

chloride per 1,000 parts by weight of mixed claims to the cold reaction mixture 'in' the, form of a solution of the aluminum chloride in methyl chloride, approximately200 parts by weight of methyl chloride being used. I

In each instance, thereactor was cooled toa temperature wellbelow 0., and there'wer'e then added approximately 10 partsof-a mixture of 97% of isobutylene of 98% purity with 3% of" isoprene of 96% purity, and there were then' added 2 or 3 parts by weight of the alkane chlorofluoride.

The'solution of aluminum chloride in methyl chloride'was added through anozzle under pressure into the body of the rapidly stirred reaction mixture, the addition of catalyst occupying approximately 6 minutes in time (althoughinother instances the time of addition was varied without change in the reaction between 2 minutes and 8 minutes). It was noted that immediately after the catalyst addition was begun, the liquid became translucent, forming a milk white suspension of very fine polymer particles. After 2 or 3 minutes, the reaction suddenly became much more vigorous, and continued for about 5 minutes after the catalyst injection had been completed. Vigorous stirring was continued during the entire time of the addition of the catalyst, and for a period of approximately 20 minutes thereafter. At the close of this time, the contents of the reactor were in the form of a slurry or emulsion of polymer particles in the alkane chloro-fluorid'e. This liquid slurry was then dumped into warm water to volatilize out the residual unsaturates, the methyl chloride, catalyst solvent and the I 7 alkane chloro fiuoride, and at the same time to quench the catalyst. The resulting polymer ret mained in the form of a moderately fine grained slurry in the water. It was readily separated from the water by a strainer and was then transferred to an open roll mill.

The results are shown in the following table. In each instance the olefinic material consisted of a mixture of three parts of isoprene with 97 parts of isobutylene, both of a degree of purity above about 98%. Each polymerization mixture was diluted with a volume of diluent as shown in'the table, and in each instance, comparison polymerizations were conducted, using methyl chloride for the diluent, to show the increase in unsaturation.

iodine number, but does not show the corresponding reduction in cross-linked, insoluble material.

On the mill, the solid polymer was washed with clear water to remove as much as possible of the catalyst breakdown product and polymerizate mixture residue, and was then compounded according to the following recipe:

Regular Pure Loaded Gum Recipe Recipe Parts Polymer 100 100 Carbon Black 50 10 Zinc Oxide 6 5 Stearic Acid... 3 3 Sulfur 2 l. 5 Tuads (tetra methyl thiuram uliid 1 1.0 Oaptax 0. 5

The compounded polymer was then cured in a mold under heat and pressure to obtain a cured specimen which, upon test, showed excellent physical properties. Of these properties the physical strengths were about the same, or slightly superior to the physical strengths of prior cured copolymers. The respective elongations at break and moduli also were about the same as or slightly superior to polymers of the prior art. Similarly, the flexure resistance and abrasion resistance were excellent; in addition the material showed a markedly increased curing rate, an adequate state of cure being obtained in from to the normal curing time, due in part to the higher unsaturation, in part to the freedom from insoluble material, and in part probably to some other phenomenon connected with the nature of the diluent.

These results show the excellent quality of the polymer as prepared in some of its physical properties.

Thus, the invention polymerizes a mixture of a lower mono-olefin with a lower multiolefin in the presence of a chloro-fluoro-substituted alkane to produce a polymer having a higher unsaturation and higher curing rate, and when cured, an excellent tensile strength, modulus and other properties.

While there are above disclosed but a limited number of embodiments of the process and apparatus of the present invention, it is possible to provide still other embodiments without depart ing from the inventive concept herein disclosed, and it is therefore desired that only such limitations be imposed upon the appended claims as are polymerizing the resulting mixture with a dis-' solved Friedel-Crafts catalyst, in the presence of from 1 to 10 volumes (computed upon the mixed olefins) of a liquid selected from the group consisting of dichlorodifiuormethane, trichloromonofluormethane, dichloromonofluormethane, dichlorotetrafiuorethane, and mixtures thereof, the monoolefin and multiolefin being dissolved in said liquid, and carrying out the polymerization at a temperature between -20 C. and the freezing point of the liquid, the resulting polymer being characterized by a higher unsaturation and higher curing rate.

2. A polymerization process comprising the steps in combination of mixing together a major proportion of isobutylene, with a minor proportion of a multiolefin having from 4 to 14, inclusive, carbon atoms per molecule, and polymerizing the resulting mixture with a dissolved Friedel- Crafts catalyst, in the presence of from 1 to 10 volumes (computed upon the mixed olefins) of a liquid selected from the group consisting of dichlorodifiuormethane, trichloromonofiuormeth ane, dichloromonofiuormethane, dichlorotetrafluorethane, and mixtures thereof, the isobutylene and the multiolefin being dissolved in said liquid, carrying out the polymerization at a temperature between 20 C. and the freezing point of the liquid, the resulting olymer being characterized by a higher unsaturation and higher curing rate.

3. A polymerization process comprising the steps in combination of mixing together a major proportion of isobutylene with a minor proportion of isoprene and polymerizing the resulting mix ture with a dissolved Friedel-Crafts catalyst, in the presence of from 1 to 10 volumes (computed upon the mixed olefins) of a liquid selected from the group consisting of dichlorodifiuormethane, trichloromonofluormethane, dichloromonofluormethane, dichlorotetrafluorethane, and mix-' tures thereof, the isobutylene and isoprene being dissolved in said liquid and carrying out the polymerization at a temperature between 20 C. and the freezing point of the liquid, the resulting polymer being characterized by a higher unsaturation and higher curing rate.

4. A polymerization process comprising the steps in combination of mixing together a major proportion of isobutylene, with a minor proportion of butadiene and polymerizing the resulting mixture with a dissolved Friedel-Crafts catalyst, in the presence of from 1 to 10 volume (computed upon the mixed olefins) of a liquid selected from the group consisting of dichlorodifiuormethane, trichloromonofluormethane, dichloromonofluormethane, dichlorotetrafluorethane, and mixtures thereof, the isobutylene and butadiene being dissolved in said liquid, and carrying out the polymerization at a temperature between 20 C. and the freezing point of the liquid, the resulting polymer being characterized by a higher unsaturation and higher curing rate.

5. A polymerization process comprising the steps in combination of mixing together a major proportion of a monoolefin having from 4 to 8, inclusive, carbon atoms per molecule, with a minor proportion of a multiolefin having from 4 to 14, inclusive, carbon atoms per molecule, and polymerizing the resulting mixture with a dissolved Friedel-Crafts catalyst, in solution in from 1 to volumes (computed upon the mixed olefins) of dichlorodifluoromethane, which is liquid at the polymerization temperature and volatile below the boiling point of water, and

carrying out the polymerization at a temperature between C. and the freezing point of the liquid alkane chlorofluoride, the resulting polymer being characterized by a higher unsaturation and higher curing rate. d f

6. A polymerization process comprising the steps in combination of mixing together a major proportion of isobutylene, with a minor proportion of a multiolefin having from 4 to 14, inclusive, carbon atoms per molecule, and polymerizing the resulting mixture with a dissolved Friedel- Crafts catalyst, in solution in from 1 to 10 volumes (computed upon the mixed olefins) of dichlorodifiuoromethane, which is liquid at the polymerization temperature and volatile below the boiling point of water, and carrying out the polymerization at a temperature between 20 C. and the freezing point of the liquid alkane chlorofiuoride, the resulting polymer being characterized by a higher unsaturation and higher curing rate.

7. A polymerization process comprising the steps in combination of mixing together a major proportion of isobutylene, with a minor proportion of isoprene, and'polymerizing the resulting mixture with a dissolved Friedel-Crafts catalyst,

in solution in from 1 to 10 volumes (computed upon the mixed olefins) of dichlorodifluoromethane, which is liquid at the polymerization temperature and volatile below the boiling point of water, and carrying out the polymerization at a tion of butadiene, andpolymerizing the resulting mixture with a dissolved Friedel-Crafts catalyst, in solution in from 1 to 10 volumes (computed upon the mixed oleflns) of dichlorodifiuoromethane, which is liquid at the polymerization temperature and volatile below the boiling point of I water, and carrying out the polymerization at a temperature between 20 C. and the freezing point of the liquid alkane chlorofiuoride, the resulting polymer being characterized by a higher unsaturation and higher curing rate;

JOHN S. SAYLOR, JR.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,243,470 Morway May 27, 1941 2,356,128 Thomas Aug. 22, 1944 2,534,698 Calfee Dec. '19, 1950 2,548,415

Welch Apr. 10, 1951 

1. A POLYFMERIZATION PROCESS COMPRISING THE STEPS IN COMBINATION OF MIXING TOGETHER A MAJOR PROPORTION OF A MONOOLEFIN HAVING FROM 4 TO 8, INCLUSIVE, CARBON ATOMS PER MOLECULE, WITH A MINOR PROPORTION OF A MULTIOLEFIN HAVING FROM 4 TO 14, INCLUSIVE, CARBON ATOMS PER MOLECULE, AND POLYMERIZING THE RESULTING MIXTURE WITH A DIS SOLVED FRIEDEL-CRAFTS CATALYST, IN THE PRESENCE OF FROM 1 TO 10 VOLUMES (COMPUTED UPON THE MIXED OLEFINS) OF A LIQUID SELECTED FROM THE GROUP CONSISTING OF DICHLORODIFLUORMETHANE, TRICHLOROMONOFLUORMETHANE, DICHLOROMONOFLUORMETHANE, DICHLOROTETRAFLUORETHANE, AND MIXTURES THEREOF, THE MONOOLEFIN AND MULTIOLEFIN BEING DISSOLVED IN SAID LIQUID, AND CARRYING OUT THE POLYMERIZATION AT A TEMPERATURE BETWEEN -20* C. AND THE FREEZING POINT OF THE LIQUID, THE RESULTING POLYMER BEING CHARACTERIZED BY A HIGHER UNSATURATION AND HIGHER CURING RATE. 